pyrolysis oil and upgrading sot - pacific northwest … inl has made significant advances in...

PNNL-22133

Prepared for the U.S. Department of Energy under Contract DE-AC05-76RL01830

Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: 2011 State of Technology and Projections to 2017 SB Jones JL Male February 2012

PNNL-22133

Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: 2011 State of Technology and Projections to 2017

SB Jones

JL Male

February 2012

Prepared for

the U.S. Department of Energy

under Contract DE-AC05-76RL01830

Pacific Northwest National Laboratory

Richland, Washington 99352

iii

Contents

1.0 Introduction ................................................................................................................................ 1

2.0 State of Technology for FY2011 ................................................................................................ 3

2.1 Feedstock and Feedstock Preparation ................................................................................ 3

2.2 Fast Pyrolysis ..................................................................................................................... 5

2.3 Upgrading ........................................................................................................................... 5

2.4 Hydrocracking .................................................................................................................... 7

2.5 Hydrogen Generation ......................................................................................................... 8

3.0 Progression to $2.32/gallon Minimum Fuel Selling Price (MFSP) in 2017 ............................... 9

4.0 Concluding Remarks ................................................................................................................ 13

5.0 References ................................................................................................................................ 14

Figures

Figure 1. Block Diagram – 2017 Projection Design Case ................................................................. 1

Figure 2. Block Diagram – 2011 SOT Case ...................................................................................... 3

Figure 3. Block Diagram – Original Design Case Pyrolysis Section................................................. 3

Figure 4. Block Diagram – Updated Design Case Pyrolysis Section ................................................ 4

Tables

Table 1. Pyrolysis Oil Characterization ............................................................................................. 5

Table 2. Stable Hydrocarbon Oil Production ..................................................................................... 6

Table 3. SOT Standalone Plant ........................................................................................................ 10

1

1.0 Introduction

In February 2009, the Pacific Northwest National Laboratory (PNNL) and the National Renewable

Energy Laboratory (NREL) produced a report detailing the process design and economic analysis for the

thermochemical conversion of biomass (wood) into gasoline and diesel (Jones et al 2009). The purpose

of the design report is to establish a research goal benchmark case for renewable fuels production in the

2017 timeframe. Annual technical and cost targets have been established and documented in the DOE

Biomass Program’s Multi-Year Program Plan. Progress towards the 2017 goals are assessed annually.

The purpose of this report is to document the review of the 2011 state of technology (SOT) and any

revisions to the projections to 2017 as reported in the November 2011 Biomass Multi-Year Program Plan

(DOE 2011).

This is a conceptual process design for converting biomass into fuels that achieves key technical targets in

a specified year, assuming nth plant modeled capital and operating costs, and is calculated in constant

2007 dollars.

As shown in Figure 1, the original 2017 design case flowsheet (Jones et al 2009) involves several process

steps:

Feedstock drying and size reduction (note that the figure shows the original design case flowsheet

as modeled in 2009– updates to this flowsheet are discussed in Section 2)

Conversion of wood into bio-oil via fast pyrolysis

Upgrading the fast pyrolysis oil to a stable hydrocarbon oil by two-stage hydrotreating to remove

oxygen

Distillation of the stable hydrocarbon oil into gasoline and diesel products

Hydrocracking the heavier- than- diesel fraction (‘heavies”) into additional gasoline and diesel.

Figure 1. 2017 Projection Design Case Block Flow Diagram

Drying and

Size

Reduction

Fast

Pyrolysis

Off -gas2-step

Hydrotreating

Product

Separation

Gasoline

Heavies

Supplemental

Natural Gas

Ash

Exhaust

Vent

Steam

ReformingHydrogen

Stable

Oil

Wastewater

Combustion

Exhaust

Combustion

Exhaust

Hydrocracking

and Product

Separation

Hydrogen

Gasoline

Diesel

Fast

Pyrolysis

Oil Diesel

2

The purpose of the state of technology is to serve as an annual assessment of the progress toward the

projected 2017 goals. It is based on the best publically available data, in terms of key technical

parameters and nth plant modeled capital and operating costs. Thus it is not a calculation of the current

commercial cost of production for the products for a pioneer plant.

3

2.0 State of Technology for FY2011

Figure 2 shows the simplified flow for the current state of technology. The diesel and heavier portion of

the stable hydrocarbon oil requires further finishing in a hydrocracker.

Figure 2. Block Diagram – 2011 SOT Case

2.1 Feedstock and Feedstock Preparation

Based on work by the Oak Ridge National Laboratory (ORNL) and the Idaho National Laboratory (INL),

it is assumed that wood is available at $82/dry short ton in 2011 (DOE 2011). At this price, the wood has

been dried and sized and needs no further preparation prior to fast pyrolysis. The 2017 Design Case

published in 2009 (shown in Figure 1) assumed that the feedstock arrives at the plant gate as 50%

moisture wood chips. A portion of the conversion cost involved drying the feedstock to 7% moisture and

reducing the wood size to 2 – 6 mm particles as shown in Figure 3.

Figure 3. Block Diagram – Original Design Case Pyrolysis Section

Fast

PyrolysisWood

2-step

Hydrotreating

Product

Separation

Gasoline

Diesel +

Heavies

Stable

Oil

Hydrocracking

and Product

Separation

Gasoline

Diesel

Fast

Pyrolysis

Oil

50% Moisture

Wood Chips

Battery Limits

7% Moisture

2-6 mm wood flour

DRYER GRINDER

PYROLYZER

CYCLONE

SAND HEATER

CONDENSER

Pyrolysis Oil

Offgas

Sand

Char &

Sand

Pyrolysis

Vapors

Sand Heater Exhaust

To atmosphere

Fluidizing Gas

4

INL has made significant advances in understanding feedstock preparation and its associated costs. Field

drying and improved storage reduces the wood chip moisture content to 30% without the use of a dryer.

As such, the current feedstock cost projections assume pyrolysis reactor throat ready feedstock that has

been dried from 30% moisture to 10% moisture and ground to 2-6 mm particles outside of the battery

limit of the conversion process. Thus the 2009-2011 SOT models and the 2012-2017 projection models

were revised to reflect these changes. This is shown in Figure 4.

Figure 4. Block Diagram – Updated Design Case Pyrolysis Section

The reduced need for drying allows all of the off-gas from the pyrolysis reactor to be sent to the hydrogen

plant rather than the biomass dryer. This eliminates some of the need for supplemental natural gas and

hence reducing green house gas (GHG) emissions. Additionally, some of the heat from the char burner

can be recuperated for process needs in the conversion plant. Finally, commercial pyrolysis reactor costs

have been published since the 2009 Design Case, allowing for a review of the pyrolysis reactor costs from

publically available data. The summary of these changes and their impact on the conversion costs are:

Capital cost changes:

• Remove dryer and grinder costs from conversion (costs ↓)

• Add heat recovery and compressed air costs (costs ↑)

• Update pyrolysis reactor costs to use publically available commercial cost data (costs ↑)

Operating cost changes

• Reduced natural gas consumption because of availability of pyrolysis off-gas (costs ↓)

• Removed duplicative power consumption for grinding (costs ↓)

• Improved GHG footprint because of reduced need for natural gas in the hydrogen plant

(GHG estimate work ongoing).

The resulting net cost changes are within 10% of the 2017 Conversion Target. Thus the 2017 cost target

remains unchanged.

30% Moisture

Wood Chips

Battery Limits

10% Moisture

2-6 mm w ood flour

PYROLYZER

Pyrolysis Oil

Offgas

Sand

Char &

Sand

Pyrolysis

Vapors

Sand Heater

Exhaust

To

atmosphere

Air

DRYER GRINDER SAND HEATER

CONDENSER

Fluidizing Gas

Offgas to

H2 Plant

BOILERBFW PREHEAT

CYCLONE

5

2.2 Fast Pyrolysis

Conventional non-catalyzed fast pyrolysis is already commercialized on a small scale. The largest

circulating fluidized bed is 400 dry metric tpd unit as built by Ensyn (Envergent 2011). The 2011 case

assumes a single 2000 dry metric tpd pyrolyzer and the associated economy of scale. Heat transfer

limitations may make this degree of scale-up difficult to achieve and evaluation of multiple parallel units

will be considered in future work. The assumed yields of gas, oil, water and char are shown in Table 1:

Table 1. Pyrolysis Oil Characterization

2011 2017

Yields, lb/100 lb dry wood

Oil 60 65

Water 11 10

Char & Ash 16 13

Gas 13 12

Key Research Areas for Conventional Fast Pyrolysis Oils:

High oxygen content, storage instability, particulates and corrosiveness all contribute to downstream

upgrading difficulties. Mitigating these effects involves understanding or achieving:

Reduced oxygen content in pyrolysis oil (possibly through catalysis).

Effective ash and particulates removal from the pyrolysis oil.

Sulfur, nitrogen and other contaminant species distribution among the gas, liquid, and char.

Prediction and reduction of corrosion potential. Materials of construction significantly impact

plant capital and maintenance costs. There is a need for a new test that measures the corrosion

tendencies of pyrolysis oil. The total acid number (TAN) measure is used to measure naphthenic

acids in crude oils, and hence the propensity for corrosion. TAN does not adequately indicate

corrosiveness in fast pyrolysis oil because it also measures non-acidic oxygenated species, such

as phenols. Thus it is necessary to develop a new test that addresses corrosion tendencies in this

type of oil. It has been found that TAN correlates to total volatile acids (Oasmaa, et al 2009),

which may be a way to quickly assess bio-oil corrosion potential.

Process fundamentals. Fast pyrolysis is a non-equilibrium process and bio-oil properties are a

function of temperature, pressure, residence time, reactor configuration and quench method.

Computational Fluid Dynamic (CFD) coupled with kinetics and reaction mechanisms may enable

a pathway to understand the formation of product species and assist reactor design and scale-up,

however, this challenge is not-trivial due to the complexity of the reactive matrix and the

possibility of a significant number of cross reactions.

2.3 Upgrading

Hydrotreating removes oxygen as well as nitrogen and sulfur. It can also saturate olefins, aromatics, and

finally will completely deoxygenate phenolics depending upon the severity of the operation. Upgrading

6

fast pyrolysis oil to stable hydrocarbon oil occurs in two steps. The first reactor step uses mild

hydrotreating conditions to remove some of the oxygen and prevents secondary reactions (such as

polymerization) that lead to catalyst deactivation. The second reactor operates at greater severity than the

first; it uses higher temperatures and/or lower space velocities to achieve low levels of oxygen (<1 wt %).

One of the advantages of the upgrading process is that it can be tailored to meet different ratios of

gasoline, jet and diesel. For example, UOP proposed a combined hydrotreating/hydrocracking reactor

that produces 15% lights, 30% gasoline and 8% diesel range boiling material. The gasoline has good

octane, while the diesel has low cetane due to high aromatics content (Holmgren 2008). Alternatively,

Veba Oel employed severe hydrotreating without hydrocracking to produce a 99% deoxygenated product

that is approximately 40% naphtha, 40% diesel and 20% heavy material and contains less than 0.5%

oxygen. The diesel boiling range has good cetane (>40) but the lighter material in the naphtha range has

low octane (Elliott 2007). Current research performed by PNNL and NREL studied the properties of

various boiling point cuts from bio-oil that were hydrotreated to different oxygen levels (Christensen et al

2011). The octane value of the naphtha cut decreased with decreasing levels of residual oxygen. Cetane

was not measured for the middle distillates cut, however, this cut at low oxygen levels (<0.4 wt%)

appears to be a very good candidate for jet fuel production. The product distribution for the low oxygen

product was approximately 44% for lights plus naphtha, 43% for distillates and 13% for gasoil. The

process chosen for the design case is assumed to balance the gasoline and diesel range products. The

state of technology is such that good gasoline range octane and good diesel range cetane are not

simultaneously produced without additional hydrotreating of the diesel and higher boiling range material.

Future techno-economic assessments might investigate maximization of products in the diesel and jet

boiling ranges, in response to market drivers and gradual shifts toward electrification.

Upgrading in the 2011 SOT case is based on laboratory generated data and reflects the short period of

time before the catalyst must be completely replaced. Parallel reactors are used to meet the 90% stream

factor. Reactor end-of-run occurs when the reactor pressure drop rises substantially and/or the catalyst

activity declines. At that point the reactor is taken off-line, while the standby reactor is brought into

service. A portion of the offline reactor’s catalyst is replaced with fresh catalyst and a portion discarded.

Catalyst disposal is required until an effective means of regenerating carbon- based catalysts is found. To

date, at best, the original charge of catalyst will last approximately one month before it is completely

replaced.

Product quality is obviously important. Gasoline range octane is preserved, but the diesel exhibits poor

cetane due to under-hydrogenation. Thus, the diesel and heavier boiling range material requires further

hydrotreating. A possible alternate product is the stable hydrocarbon oil itself, which could be sold as a

fuel oil substitute for bioenergy. Further examination of the value proposition in this application is

currently beyond the scope of this SOT.

The stable hydrocarbon oil annual production rate currently achieved and the 2017 projection is shown in

Table 2.

Table 2. Stable Hydrocarbon Oil Production

Annual Production 2011 2017

Gasoline+Diesel, 106 gal/year 53 76

7

Key Research Areas for Upgrading Conventional Fast Pyrolysis Oils:

Upgrading pyrolysis oil to infrastructure compatible fuels can take many routes (Elliott 2007). Recent

studies have begun to look at the details of these routes (Elliot et al 2009, Venderbosch et al 2009,

Christensen et al 2011). The key research areas for conventional fast pyrolysis oil upgrading are catalyst

life, efficient usage of hydrogen, and product quality. This involves understanding:

How upgrading conditions affect product quality, e.g. temperature, pressure, space velocity,

hydrogen partial pressure at the reactor outlet.

The effect of catalyst type and support affect product quality and yield, e.g. conventional

hydrotreating catalysts versus palladium or ruthenium, alumina supports versus carbon.

The effective concentration of hydrogen on the surface of the catalyst.

Catalyst deactivation mechanisms, which likely are a combination of coke formation, catalyst

sintering, and catalyst poisoning or occlusion.

Reaction kinetics to allow improved reactor design and potential reduction in capital expenditure

together with control of competing mechanisms in order to improve selectivity towards desired

products.

There is also a significant need for detailed data regarding the characteristics of the stable hydrocarbon

oil. In particular:

Boiling point curves, density, heating value, and ultimate analysis for the stable hydrocarbon oil

product and each product cut from the hydrocarbon oil (lights, naphtha, jet, diesel, gasoil).

Cetane and octane values for the naphtha and diesel cuts.

Yields for each product cut.

Relative reaction rates of different functional groups within the bio-oil as it relates to the catalyst,

the reactants and on the reactor surface.

Compound types (e.g., % oxygenates, aromatics, naphthenes, olefins and saturates) within each of

the product cuts.

2.4 Hydrocracking

Hydrocracking creates smaller chain components from larger ones and saturates alkenes and aromatics. It

also removes any remaining oxygenates, such as the phenolic type groups which appears to be the most

difficult oxygenate type to remove (Christensen et al 2011). The 2011 SOT case requires that all of the

diesel and heavier boiling range product be finished in a hydrocracker. This treatment cracks the heavier-

than-diesel components back to the diesel range and removes residual olefins, aromatics and oxygenates.

Key Hydrocracking Research Areas:

Standalone hydrocracking is not currently a part of the core research work. However, meeting diesel

range properties and yield requires the understanding of:

The extent of additional hydrotreating needed to improve diesel properties to acceptable levels

(aromatic content of less than 25% and cetane index of at least 40).

The operational ability to adjust yields between the naphtha, jet and diesel boiling ranges.

8

2.5 Hydrogen Generation

Off-gas from the fast pyrolysis section, the upgrading reactors and the hydrocracker, supplemented with

natural gas, is sent to a steam reformer to generate the hydrogen used in the upgrading reactors. As

natural gas is not renewable, an alternative means of hydrogen generation may be desirable if

economically viable. For example, renewable hydrogen could be produced by reforming a portion of the

whole fast pyrolysis oil or a fractionated portion of the oil. This option was not considered in the 2017

design case, but will be included in a future update.

Key Hydrogen Generation Research Areas:

Hydrogen generation from natural gas is well established and easily the least expensive form of hydrogen

production. However, steam reforming of whole or fractionated pyrolysis oil is being researched by

NREL under the Hydrogen Program. Catalyst life and performance are the key issues (Czernik 2007).

9

3.0 Progression to $2.32/gallon Minimum Fuel Selling Price (MFSP) in 2017

It is possible to meet individual targets separately, such as good gasoline octane, or low hydrogen

consumption or low oxygen content. However, the research challenges are to simultaneously make good

quality gasoline and diesel blendstocks, while balancing hydrogen consumption with yield, and

maximizing upgrading catalyst life. Table 3 shows the MFSP for the 2011 SOT and the progression to

the 2017 design case. All costs are in 2007 constant dollars.

Previous design cases for ethanol were able to report costs on an individual product basis, i.e., the

minimum ethanol selling price (MESP). Since the pyrolysis case produces two products (possibly three if

a jet fuel cut is made), there is a need to determine a minimum selling price for each fuel. The

methodology to produce separate cost breakouts for gasoline and diesel was achieved in two steps:

calculating the minimum selling price for the combined volumes of gasoline and diesel, then separating

the capital and operating costs that are specific to each fuel. The production process for both gasoline and

diesel in the 2011 SOT are the same all the way up through the two upgrading reactors and initial product

separation. After that, the gasoline cut is essentially finished, but the diesel cut needs additional

hydrotreating and the heavier than diesel cut requires hydrocracking. Thus the cost for additional diesel

upgrading is assigned only to the diesel fraction. As the technology improves, the diesel fraction will

need less and less additional upgrading and the cost of producing gasoline and diesel should approach one

another. This improvement effect is reflected in the 2017 production costs being the same for both

products.

Table 3 shows the research targets needed to advance from the current SOT to the 2017 goal. In the early

years, the focus is on improving the upgrading catalyst life. This is reflected in the high cost of fuel

production – a result of additional spare equipment needed to mitigate the effects of significant catalyst

makeup. In later years, the focus shifts to increasing the product yield.

In addition to the research advances expected from the core pyrolysis and upgrading work, there are

several new projects resulting from solicitations that are expected to provide technology breakthroughs.

Two examples are the National Advanced Biofuels Consortium (NABC 2010) and the pyrolysis and

upgrading solicitation awards (DOE 2010). There is other research funded by other agencies and

departments of DOE. These projects are exploring variations/alternatives to fast pyrolysis to generate

bio-oil that is subsequently upgraded to a hydrocarbon. Examples of these are catalytic pyrolysis (in both

the liquid phase and/or the vapor phase), hydrothermal liquefaction, and hydro-pyrolysis. These

pathways produce different quality bio-oils and may require different, possibly less severe, upgrading to

hydrocarbon oil than that described in the conventional fast pyrolysis and upgrading design case. Thus,

the heavy, dark green vertical line separating the years 2012 and 2013 indicates the provision to reassess

the goals in Table 3 with respect to findings from the NABC and the upgrading solicitation. It is expected

that a new design case will be published as a result.

10

Table 3. SOT Standalone Plant

Processing Area Cost

Contributions & Key Technical

Parameters Metric 2009 SOT 2010 SOT 2011 SOT

2012

Projection

2013

Projection2

2014

Projection

2015

Projection

2016

Projection

2017

Projection3

$/gal gasoline $6.30 $4.92 $3.99 $3.51 $2.82 $2.41 $2.26 $1.81 $1.56

$/gal diesel $6.37 $4.99 $4.06 $3.57 $2.90 $2.48 $2.33 $1.88 $1.56

Conversion Contribution,

combined fuel $/gge $6.02 $4.71 $3.83 $3.38 $2.71 $2.32 $2.18 $1.75 $1.47

Year $ basis 2007 2007 2007 2007 2007 2007 2007 2007 2007

Gasoline/Diesel 2017 EIA

Derived Forecast1 $/gal $2.85

Minimum Gasoline Selling Price $/gal gasoline $7.64 $6.21 $5.12 $4.50 $3.68 $3.27 $3.06 $2.56 $2.32

Minimum Diesel Selling Price $/gal diesel $7.72 $6.29 $5.19 $4.57 $3.76 $3.34 $3.13 $2.63 $2.32

Production Gasoline + Diesel mm gallons/yr 53 53 53 53 61 61 66 70 76

Yield (Gasoline + Diesel) gal/ dry ton wood 73 73 73 73 84 84 91 98 106

Natural Gas Consumption SCF/dry ton wood 1,840 1,840 1,650 1,650 3,820 3,820 4,140 4,450 4,430

Feedstock

Total Cost Contribution $/gal total fuel $1.33 $1.28 $1.13 $0.99 $0.85 $0.85 $0.79 $0.73 $0.75

Capital Cost Contribution $/gal total fuel $0.00 $0.00 $0.00 $0.00 $0.00 $0.00 $0.00 $0.00 $0.00

Operating Cost Contribution $/gal total fuel $1.33 $1.28 $1.13 $0.99 $0.85 $0.85 $0.79 $0.73 $0.75

Feedstock Cost $/dry US ton $96.65 $93.10 $82.00 $71.97 $71.97 $71.97 $71.97 $71.97 $79.37

Energy Content (LHV, dry basis) BTU/lb 7603 7603 7603 7603 7603 7603 7603 7603 7603

Table B-6: Unit Operation Cost Contribution Estimates (2007$) and Technical Projections for Thermochemical Conversion to

Gasoline and Diesel Baseline Process Concept

(Process Concept: Woody Energy Crop, Fast Pyrolysis, Bio-oil Upgrading, Fuel Finishing)

Conversion Contribution

11




2012

Projection

2013

Projection2

2014

Projection

2015

Projection

2016

Projection

2017

Projection3

$/gal gasoline $6.30 $4.92 $3.99 $3.51 $2.82 $2.41 $2.26 $1.81 $1.56

$/gal diesel $6.37 $4.99 $4.06 $3.57 $2.90 $2.48 $2.33 $1.88 $1.56



Year $ basis 2007 2007 2007 2007 2007 2007 2007 2007 2007








Feedstock









Conversion ContributionFast Pyrolysis




Feed Moisture Content to FP % 10% 10% 10% 10% 10% 10% 10% 10% 10%

Number Fast Pyrolysis Units

1x2000 tpd no

filter

1x2000 tpd no

filter

1x2000 tpd

w filter

1x2000 tpd

w filter

1x2000 tpd

w filter

1x2000 tpd

w filter

1x2000 tpd

w filter

1x2000 tpd

w filter

1x2000 tpd

w filter

Pyrolysis Oil Yield (dry) lb/lb dry wood 0.60 0.60 0.60 0.60 0.62 0.62 0.63 0.64 0.65

Ash Content ppm <500 <500 <500 <500 <500 <500 <500 <500 <500

Char ppm <500 <500 <500 <500 <500 <500 <500 <500 <500

Corrosivity, TBD TBD TBD TBD TBD TBD TBD TBD TBD TBD TBD

Upgrading to Stable Oil via Multi-Step Hydrodeoxygenation




Number of Parallel Hydrotreaters

2x100% w

guard bed

2x100% w

guard bed

2x100% no

guard bed

2x100% no

guard bed

2x100% no

guard bed

2x100% no

guard bed

2x100% no

guard bed

1x100% no

guard bed

1x100% no

guard bed

Catalyst Life operating days 14 21 30 40 60 120 120 329 329

Catalyst Regeneration Frequency days 0 0 0 0 0 0 0 6 1

Catalyst Base carbon carbon carbon carbon carbon carbon carbon carbon carbon

Stable Oil Yield lb/lb dry FP oil 0.40 0.40 0.40 0.40 0.45 0.45 0.47 0.50 0.55

Corrosivity, TBD TBD TBD TBD TBD TBD TBD TBD TBD TBD TBD

Sulfur ppm <40 <40 <40 <40 <40 <30 <30 <20 <15

Nitrogen ppm <40 <40 <40 <40 <40 <40 <40 <40 <40

Chlorine ppm <50 <50 <50 <50 <50 <50 <50 <50 <50

Alkali Compounds ppm <10 <10 <10 <10 <10 <10 <10 <10 <10

Gasoline, Octane Number ~89 ~89 ~89 ~89 ~89 ~89 ~89 ~89 ~89

Diesel, Cetane Index ~32 ~32 ~32 ~32 ~32 ~32 ~32 ~32 >40

Hydrogen Partial Pressure Reactor psia ~1750 ~1750 ~1600 ~1600 ~1600 ~1600 ~1600 ~1600 ~1600

12




2012

Projection

2013

Projection2

2014

Projection

2015

Projection

2016

Projection

2017

Projection3

$/gal gasoline $6.30 $4.92 $3.99 $3.51 $2.82 $2.41 $2.26 $1.81 $1.56

$/gal diesel $6.37 $4.99 $4.06 $3.57 $2.90 $2.48 $2.33 $1.88 $1.56



Year $ basis 2007 2007 2007 2007 2007 2007 2007 2007 2007








Feedstock









Conversion ContributionFuel Finishing to Gasoline and Diesel via Hydrocracking and Distillation




Extent of Hydrocracking/treating

diesel and

heavier

diesel and

heavier

diesel and

heavier

diesel and

heavier

diesel and

heavier

diesel and

heavier

diesel and

heavier

diesel and

heavier

heavier than

diesel

Balance of Plant: Hydrogen Generation & OSBL




Models: Case References2009 SOT-

1011

2010 SOT-

1011

2011 SOT-

10112012 P-1011 2013 P-1011 2014 P-1011 2015 P-1011 2016 P-1011

2017 Design

1011

Note: The table may contain very small (< $0.01) rounding errors due to the difference betw een the w ay that Microsoft Excel™ displays and calculates rounded values.1EIA, “Annual Energy Outlook 2009" Post ARRA April 2009, Table 112, U.S., ,” Table 112, U.S., April 2009, http://w w w .eia.doe.gov/oiaf/archive/aeo09/supplement/suptab_112.xls2The demarcation line betw een 2012 and 2013 indicates the design case update planned to incorporate f indings from the NABC, the stabilization call, and future upgrading w ork3"Production of Gasoline and Diesel from Biomass Via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case", PNNL-18284, February 2009

13

4.0 Concluding Remarks

In order to be on a trajectory to a modeled nth plant $2.32/ gallon of fuel in 2017 (feedstock cost of $79.37

/dry U.S. ton, 2007$) a modeled Minimum Gasoline Selling Price of $5.12/gallon of gasoline or

Minimum Diesel Selling Price of $5.19/gallon of diesel was experimentally determined in 2011.

Technically this was attained through bench scale experimental demonstration to show a combined

gasoline and diesel blend stock yield of 73 gallons/dry U.S. ton and a catalyst replacement lifetime of 30

operating days.

The further research needed to achieve the 2017 goal of $2.32/gal fuel (2007$) is summarized as follows:

Improve the quality and consistency of bio-oil.

Develop the means to extend the life of the pyrolysis oil upgrading catalysts, for example,

through improved filtering, refinement of catalyst design, and optimized upgrading conditions.

Develop a better understanding of reactor limitations and opportunities by developing predictive

pyrolysis-oil production models and upgrading the reactor models to replace the stoichiometric

models used in the design case study.

Conduct catalyst deactivation studies to understand the mechanisms responsible for short

upgrading catalyst life.

Determine stable oil and product fuel specifications for oil refinery acceptance and how to

maximize cuts or blends of upgraded fuels to balance production in existing refineries.

Incorporation of the new concepts generated by the core work, NABC, Integrated Bio

Refineries (IBRs) and upgrading solicitation work into economic assessments of future cases for

biomass pyrolysis should be the next stage of analysis. Advanced pyrolysis processes may

include:

New reactor system engineering involving improved heat transfer mechanisms and catalyst

maintenance.

Pyrolysis including in-situ catalysis and vapor phase catalysis with or without the presence of

externally added hydrogen.

Post pyrolysis processing to improve product bio-oil properties.

Post-process separations and subsequent treatment to produce improved products.

Greater effective hydrogen concentration on the surface of the upgrading catalyst.

Higher efficiency integrated systems with improved heat utilization.

14

5.0 References

Christensen, et al, “Analysis of Oxygenated Compounds in Hydrotreated Biomass Fast Pyrolysis Oil

Distillate Fractions” Energy & Fuels, 25 (2011) 5462-5471

Czernik, S, R. Evans, and R. French, “Hydrogen from Biomass-Production by Steam Reforming of

Biomass Pyrolysis Oil” Catalysis Today,129 (2007) 265-268

U.S. Department of Energy. 2011. Biomass Multi-Year Program Plan. Office of the Biomass Program,

Energy Efficiency and Renewable Energy, U.S. Department of Energy, Washington D.C.

U.S. Department of Energy. 2010. Advanced Biofuels Technology Development

http://www1.eere.energy.gov/biomass/news_detail.html?news_id=16311

Envergent 2011. http://www.envergenttech.com

Elliott, DC. 2007. “Historical Developments in Hydroprocessing Bio-oil.” Energy & Fuels 21:1792-1815.

Elliott, D.C., T.R. Hart, G.G. Neuenschwander, L.J. Rotness, A.L. Zacher, 2009. “Catalytic

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